Container having excellent slipping property for fluid contents

ABSTRACT

A container for containing fluid substance as a content, wherein a container surface that comes in contact with the content is formed of a resin composition that contains a forming-resin and an immiscible-liquid that is immiscible with the fluid substance. The container has markedly improved slipping property for the fluid contents and can be easily produced.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Rule 53(b) Continuation of U.S. application Ser.No. 14/763,268 filed Jul. 24, 2015, which is a National Stage ofInternational Application No. PCT/JP2014/052879, filed Feb. 7, 2014,which claims priority from Japanese Patent Application No. 2013-023468,filed Feb. 8, 2013, the contents of all of which are incorporated hereinby reference in their entirety.

TECHNICAL FIELD

This invention relates to a container having excellent slipping propertyfor fluid content and, particularly, for highly viscous fluid contents.

BACKGROUND ART

Plastic containers are easy to form, can be inexpensively produced andhave, therefore, been widely used in a variety of applications.Specifically, an olefin resin container of the shape of a bottle ofwhich the inner wall surface is formed by using an olefin resin such aslow-density polyethylene and which is formed by direct blow-forming, hasbeen desirably used as a container for containing viscous slurry-like orpaste-like fluid contents such as ketchup and the like from such astandpoint that the content can be easily squeezed out.

Further, the bottles containing highly viscous fluid contents are, inmany cases, preserved in an inverted state to quickly discharge thecontents or to use the contents to the last drop without leaving them inthe bottle. It is, therefore, desired that when the bottle is inverted,the viscous content quickly falls down without adhering or staying onthe inner wall surface of the bottle.

To satisfy such requirements, for example, a patent document 1 proposesa bottle of a multilayer structure of which the innermost layer isformed from an olefin resin having an MFR (melt flow rate) of not lessthan 10 g/10 min.

The innermost layer of this multilayer structure bottle has excellentwettability for the oily content. Therefore, if the bottle is invertedor is tilted, then the oily content such as mayonnaise or the like fallsdown spreading along the surface of the innermost layer and can becompletely discharged without adhering or remaining on the inner wallsurface of the bottle (on the surface of the innermost layer).

As for the bottles for containing viscous non-oily contents in whichplant fibers are dispersed in water like ketchup, a patent document 2and a patent document 3 are disclosing polyolefin resin bottles havingan innermost layer which is blended with a saturated or unsaturatedaliphatic amide as a lubricating agent.

The above patent documents 1 to 3 are all trying to improve slippingproperty of the plastic containers for the contents based on thechemical compositions of the thermoplastic resin compositions formingthe inner surfaces of the containers, and are achieving improvements inthe slipping property to some extent. However, limitation is imposed onimproving the slipping property due to limitation on the kinds of thethermoplastic resins that are used and on the additives, and strikingimprovement has not been achieved yet.

On the other hand, a patent document 4 is proposing a packing materialof a composition comprising 100 parts by weight of a polyolefin resinblended with an additive having an HLB of not more than 5.0 in an amountin a range of 0.3 to 3 parts by weight.

The packing material of the patent document 4 exhibits excellent partingproperty relative to emulsified contents such as chocolate creams andcustard creams. Namely, the packing material permits emulsified contentsto adhere little and alleviates such an inconvenience that the contentadheres in large amounts to the inner surface of, for example, a lidmember.

According to the study by the present inventors, however, it was foundthat the container formed from such a composition is not still capableof exhibiting slipping property to the fluid contents such as sauce andthe like.

Further, the present inventors have previously proposed a packingcontainer filled with a content, wherein at least part of the surfacethat comes in contact with the content is a liquid-permeable surfacewhich holds a liquid different from the content (Japanese PatentApplication No. 2012-157744).

This container exhibits very improved slipping property to the fluidcontents such as ketchup, sauce, mayonnaise and the like accompanied,however, by a problem in that after the container is formed, the liquidmust be applied to the portion that comes in contact with the content.Therefore, a further improvement is necessary.

PRIOR ART DOCUMENTS Patent Documents

Patent document 1: JP-A-2007-284066

Patent document 2: JP-A-2008-222291

Patent document 3: JP-A-2009-214914

Patent document 4: JP-A-6-345903

OUTLINE OF THE INVENTION Problems that the Invention is to Solve

It is, therefore, an object of the present invention to provide acontainer that has markedly improved slipping property for the fluidcontents and that can be easily produced.

Means for Solving the Problems

The present inventors have conducted experiments extensively concerningthe slipping of the fluid contents on the container wall surface. As aresult, the inventors have discovered the fact that in a containerformed by using a resin composition blended with a liquid immisciblewith the fluid content, the liquid segregates on the surface of thecontainer and works as a lubricating layer enabling excellent slippingproperty to be expressed, and have thus completed the present invention.

That is, according to the present invention, there is provided acontainer for containing fluid substance as a content, wherein acontainer surface that comes in contact with the content is formed of aresin composition that contains a forming-resin and an immiscible-liquidthat is immiscible with the fluid substance.

In the present invention, the following embodiments can be preferablyemployed.

-   (1) The covering ratio F with the immiscible-liquid is not less than    0.26, the covering ratio F being represented by the following    formula (1),

F=(cos θ−cos θ_(B))/(cos θ_(A)−cos θ_(B))

-   -   wherein θ is a water contact angle on the container surface        formed of the resin composition,    -   θ_(A) is a water contact angle on the immiscible liquid, and    -   θ_(B) is a water contact angle on the forming-resin;

-   (2) The resin composition contains the immiscible liquid in an    amount of not less than 3% by weight;

-   (3) When the container surface formed of the resin composition is    measured for its shape by using an atomic force microscope, dents    that are denting over a scanning range of 100 μm×100 μm are    observed, and in a binary image of high portions (protuberances) and    low portions (dents) with the center surface as reference converted    from the surface profile that is obtained, the average area of    protuberances over the scanning range is not less than 50 μm²;

-   (4) In the surface shape profile obtained by scanning the range of    100 μm×100 μm by using the atomic force microscope, the container    surface formed of the resin composition has a mean square surface    roughness RMS represented by the following formula (2),

$\begin{matrix}{{{RM}\; S} = \sqrt{\frac{1}{n}{\sum\limits_{i}^{n}\left( {{Z(i)} - Z_{ave}} \right)^{2}}}} & (2)\end{matrix}$

-   -   wherein n is a number of data points,    -   Z(i) is a Z value at each of the data points, and    -   Zave is an average value of all Z values, in a range of 80 nm to        200 nm;

-   (5) The container has a multilayered structure on condition that the    container surface that comes in contact with the content is formed    of the resin composition;

-   (6) Polyolefin is used as the resin for forming;

-   (7) The fluid substance used as the content has a viscosity at    25° C. of not less than 100 cps;

-   (8) The fluid substance used as the content is a non-emulsifying    aqueous substance;

-   (9) The non-emulsifying aqueous substance is a ketchup or sauce;

-   (10) A silicone oil, a glycerin fatty acid ester, a fluidized    paraffin or an edible fat and oil is used as the immiscible liquid;    and

-   (11) The resin composition is, further, coated with an immiscible    liquid.

In the invention, the fluid substances stand for those of which theshape easily varies when a force is exerted on them in their stationarystate, and excludes gelatinous materials such as some kinds of yogurtsand custard puddings or those that retain their shapes to some extent intheir stationary state, such as creams, butter and cheese.

Effects of the Invention

In the container of the present invention for containing fluid substanceas a content, a great feature resides in that at least the inner surfaceof the container that comes in contact with the content is formed of aresin composition that contains a forming-resin and a liquid (oftencalled lubricating liquid) having no affinity to the fluid substance(i.e., fluid content).

That is, the inner surface of the container is formed by using the resincomposition that contains lubricating liquid and, therefore, exhibitsexcellent slipping property for the highly viscous fluid contents suchas sauce and mayonnaise as will be demonstrated in Examples appearinglater. For example, if the container such as bottle is held in aninverted state, the content falls down in short periods of time.Besides, the content is effectively prevented from staying being adheredon the container inner surface and can, therefore, be effectively takenout from the container.

Further, for imparting lubricating property, the lubricating liquid isused being mixed with the forming-resin in advance obviating, therefore,the need of applying the lubricating liquid after the container has beenformed and hence providing advantage in producing the containers.

Moreover, the inner surface of the container is formed by using theresin composition that contains the lubricating liquid. Therefore, theinnermost layer is firmly adhered to the neighboring layer of thecontainer and is free from the probability of peeling off despite ofrepeating the squeezing operation, offering safety to a very highdegree.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are views of surface shapes on the inner surface of acontainer (Example 2) of the present invention as measured by using theatomic force microscope (scanning range of 100 μm×100 μm).

FIGS. 2A and 2B are views of surface shapes on the inner surface of acontainer (Comparative Example 1) formed by using a resin compositionwithout containing the lubricating liquid as measured by using theatomic force microscope.

FIGS. 3A and 3B are views of surface shapes on the inner surface of acontainer (Comparative Example 5) formed by using a resin composition ofwhich the surface has not been sufficiently coated as measured by usingthe atomic force microscope.

FIG. 4 is a view showing the appearance of a container of the presentinvention.

BEST MODES FOR CARRYING OUT THE INVENTION

<Principle of the Invention>

The container of the present invention has an inner surface that isformed by using a resin composition containing a lubricating liquid(i.e., a liquid immiscible with the fluid substance contained in thecontainer) and, therefore, exhibits excellent slipping property for thefluid substance (fluid content). This fact was discovered as aphenomenon as a result of extensive experiments. Though not yetclarified, the reasons are construed by the inventors to be as describedbelow.

That is, if a container is formed by using a resin compositioncontaining a lubricating liquid which is a liquid, the lubricatingliquid separates in phase away from the resin component as thetemperature decreases as a result of shaping (forming) the resincomposition into the container, and the liquid is partly exposed on thesurface. As a result, the inner surface of the container is maintainedin a state of being coated with the lubricating liquid that is exposed.Thus excellent slipping property for the fluid content is exhibited bythe lubricating liquid that is exposed on the inner surface of thecontainer.

If, for example, the inner surface of the container is formed of anolefin resin instead of the lubricating liquid, the content, when thecontainer is inverted, tends to fall down extremely less than that ofthe present invention as will be learned from the experimental resultsdemonstrated in Examples appearing later. That is, if the inner surfaceof the container is formed of the olefin resin alone, the interfacebetween the content and the inner layer of the container is asolid-liquid interface. On the other hand, if the inner surface of thecontainer is coated with the lubricating liquid to a sufficient degree,the interface is a liquid-liquid interface (i.e., contacts over a largearea to the fluid content), and the slipping property to the fluidcontent is very and strikingly improved.

At the time of forming, further, the resin is crystallized accompaniedby the phase separation of the lubricating liquid, and thecrystallization occurs at irregular rates in the surface of thecontainer which is the formed body developing fine dents in the surfaceof the container. FIGS. 1A and 1B are views of surface shapes on theinner surface of a container of Example 2 as observed by using an atomicforce microscope (100 μm×100 μm) from which black portions representingdents can be seen to be continuing. It is considered that at least partof the lubricating liquid exposed on the surface is present along thefine dents or is held in the dents. As a result, the lubricating liquidcovering the surface is firmly held therein without falling down andstably maintains the slipping property. Moreover, since fine dents havebeen continuously formed over the whole inner surface, the lubricatingliquid, even if it may not often be locally sufficient, is fed fromother portions owing to dents that are continuously present. Therefore,even if there occurs a change in the temperature or a change due tocontraction of the container, the surface can be effectively andcontinuously maintained coated with the lubricating liquid. For example,as described in Examples appearing later, the container is allowed tomaintain excellent slipping property even when it is filled with thefluid content at a high temperature. As described above, the containerwhich is formed accompanied by the phase separation of the lubricatingliquid may be coated on its surface with the lubricating liquid in asegregated manner. In this case, too, the layer of the lubricatingliquid is uniformly formed over the whole inner surface of the containeras it is formed without almost causing the layer of the lubricatingliquid to become irregular offering, therefore, a great advantage fromsuch a standpoint that excellent slipping property is homogeneouslyexhibited over the whole inner surface of the container.

<Form of the Inner Surface of the Containers>

As described above, the container of the invention has an inner surfacethat comes in contact with the fluid content, the inner surface beingformed of a resin composition containing a lubricating liquid.Therefore, the lubricating liquid is partly exposed on the inner surfaceof the container to exhibit slipping property. It is, therefore,necessary that the inner surface of the container has been coated withthe exposed lubricating liquid to a certain degree.

The ratio F of covering the inner surface of the container with thelubricating liquid can be expressed by, for example, the followingformula (1),

F=(cos θ−cos θ_(B))/(cos θ_(A)−cos θ_(B))

-   -   wherein θ is a water contact angle on the surface (inner        surface) of the container formed of the resin composition that        forms the inner surface of the container,    -   θ_(A) is a water contact angle on the immiscible liquid        (lubricating liquid), and    -   θ_(B) is a water contact angle on the forming-resin.

That is, when the water contact angle θ on the inner surface of thecontainer is the same as the water contact angle θ_(A) on thelubricating liquid, the covering ratio F is 1.0; i.e., the whole innersurface of the container is covered with the lubricating liquid. In thepresent invention, it is desired that the covering ratio F is not lessthan 0.26 and, specifically, in a range of 0.30 to 1 and, morepreferably, 0.35 to 0.91. The amount of the lubricating liquid in theresin composition is so set that the covering ratio F lies within theabove-mentioned range (the amount of the lubricating liquid will bedescribed later).

If the covering ratio F is too small, the slipping property is notexhibited to a sufficient degree for the fluid content. For instance,the packing material disclosed in the above-mentioned patent document 4exhibits no slipping property to the fluid content presumably becausethe covering ratio is small and the surfactant that corresponds to thelubricating liquid is present only in spotted manner on the surface.

Further, if the covering ratio F is too great, inconvenience may arousesuch as defective forming though there is no problem in regard to theslipping property.

In the present invention, further, being related to that the resincomposition used for forming the container inner surface has beenblended with the lubricating liquid, dents are finely and continuouslyformed in the container inner surface as will be obvious from the imageof the atomic force microscope shown in FIGS. 1A and 1B presumablycontributing to stably maintaining the slipping property.

For instance, in case the covering factor with the lubricating liquid isachieved as described above, an average area of protuberances (whiteportions) as observed through the atomic force microscope is present atan area ratio of 50 to 200 μm² and, specifically, 50 to 170 μm² over ascanning range of 100 μm×100 μm as shown in FIGS. 1A and 1B. That is,the slipping property can be maintained stable over extended periods oftime if protuberances having large areas are distributed at a suitableratio (if protuberances having small areas are much present, dents tendto be isolated and, hence, the continuity of dents decreases), i.e., ifdents are continuously distributed having large areas. In this case,further, the lubricating liquid exposed on the inner surface isprevented from falling down and favorable slipping property ismaintained even when the container is filled with the fluid content at ahigh temperature.

Further, forming the dents is reflected by the surface roughness. Forinstance, when the surface covering ratio F with the lubricating liquidlies within the above-mentioned range or when the area ratio of dents iswithin the above-mentioned range, a mean square surface roughness RMS ofthe container inner surface is, usually, in a range of 80 to 200 nm asmeasured by using the atomic force microscope over a scanning range of100 μm×100 μm, which is a very larger value than that of when the innersurface is not sufficiently covered with the lubricating liquid.

<Fluid Contents>

The content contained in the container of the present invention is afluid substance and has no specific limitation so far as it exhibitsfluidity without showing any property for holding the shape. Preferredexamples thereof, usually, include viscous paste or slurry fluidsubstances (e.g., having a viscosity at 25° C. of not less than 100cps), such as ketchup, aqueous paste, bee honey, sauces, semi-soliddressings (mayonnaise, creamy dressing for salads), emulsified liquiddressing, cosmetic liquids such as emulsion and the like, liquiddetergent, shampoo, rinse and conditioner. That is, the container of theinvention exhibits such favorable slipping property that even a viscousfluid substance can be quickly discharged without being adhered and lefton the container inner surface when it is tilted or inverted.

The container of the present invention exhibits highly slipping propertyto specifically a content having a high viscosity among the above fluidsubstances enabling the content to fall down sliding along the containerinner surface in short periods of time (high fall-down speed) and,further, enabling the content having a low viscosity to fall downthoroughly without remaining on the container inner surface.

Further, the fluid contents for which the container of the invention isused are, specifically, non-emulsion type aqueous materials such asketchup and various kinds of sauces. That is, when an emulsion typefluid substance (typically mayonnaise) is contained as the content,favorable slipping property is exhibited in the initial stage. However,as the content containing a surfactant component is repetitively causedto move along the container inner surface, the lubricating liquidexposed on the container inner surface is gradually removed by thecontent though dependent upon the kind of the lubricating liquid that iscontained, and the slipping property gradually decreases. Namely, theslipping property tends to be lost in relatively short periods of time.On the other hand, when the non-emulsion type aqueous substance iscontained, the lubricating liquid is removed very little by the content,and good slipping property is exhibited maintaining stability even whenthe container is repetitively used over extended periods of time.

<Forms of the Containers>

There is no limitation on the forms of the containers of the inventionso far as they are forming an inner surface that comes in contact withthe fluid content by using a resin composition that contains the resinfor forming the containers and the lubricating liquid. Namely, thecontainers can assume various forms such as cup, cup-like form,bottle-like form, bag (pouch), syringe, pot, tray and the like, and mayhave been stretch-formed. FIG. 4 shows an example of when the presentinvention is applied to a plastic bottle. Not being limited theretoonly, however, the containers of the invention may also be made of aglass, a paper or a metal.

Here, the container of the invention permits the content to slipexcellently and, therefore, features very excellent discharge propertyfor the content, such as inverted fall-down property for the content orpreventing the content from adhering and remaining. Therefore, thecontainer of the present invention is most desirably a direct blowmolding bottle adapted to squeezing out the viscous content such asketchup and the like.

Referring to, for example, FIG. 4, the bottle is generally designated at10, and includes a neck portion 11 having a screw thread, a body wall 15continuous to the neck portion 11 via a shoulder portion 13, and abottom wall 17 that is closing the lower end of the body wall 15. Afterthe bottle 10 is filled with a viscous content, the opening at the upperend of the neck portion 11 is heat-sealed with a metal foil 19 such asaluminum foil, and a predetermined cap 20 is fitted thereto so that thebottle is used as a packing bottle. To use the packing bottle, the cap20 is removed, the metal foil 19 applied with a sealing member is peeledoff, and the bottle 10 is tilted or inverted and, as required, the bodywall 15 is squeezed to take out the content out of the container.

<Material (Resin Composition) Forming the Container Inner Surface>

In the invention, the resin composition that forms the container innersurface contains the container-forming resin and the lubricating liquidand, further, contains suitable additives as required.

-   1. Forming-Resin.

There is no particular limitation on the forming-resin if it can beformed into the container having the inner surface of the forming-resin.There can be used a variety of thermoplastics such as polyester asrepresented by polyethylene terephthalate and olefin resin depending onthe forms of the containers.

Specifically, if the present invention is applied to the above-mentioneddirectly-blown bottle, there can be used, as the forming-resin, theknown olefin resin such as low-density polyethylene, straight-chainlow-density polyethylene, intermediate- or high-density polyethylene,polypropylene, poly 1-butene, or poly 4-methyl-1-pentene. It isallowable, as a matter of course, to use a random or block copolymer ofα-olefins, such as ethylene, propylene, 1-butene or 4-methyl-1-pentene.It is, further, allowable to use a cyclic olefin copolymer disclosed inthe above-mentioned patent document 1 (JP-A-2007-284066).

-   2. Lubricating Liquid.

As the lubricating liquid, there is used a liquid that is immisciblewith the content. If miscible with the content, the lubricating liquidexposed on the container inner surface mixes with the content andseparates away from the inner surface of the container.

Here, the liquid immiscible with the content is a liquid that is notmiscible with the content. Roughly speaking, an oleophilic liquid isused for the aqueous content while water or a hydrophilic liquid is usedfor the oily content. As the lubricating liquid, in general, there maybe used a liquid which enables the covering ratio F to lie within theabove-mentioned range (not less than 0.26) when the container is filledwith the content. Specifically, a high lubricating effect is realizedand is suited for the invention when the liquid produces a surfacetension for the inner surface of the container that is greatly differentfrom a surface tension produced by the liquid for the content.

It is, further, desired that the liquid is nonvolatile, as a matter ofcourse. Desirably, therefore, there is used a liquid that produces avapor pressure so will not to be volatilized even when the container isbeing formed or in a state where the container is exposed to theatmosphere.

As the lubricating liquid that can be most favorably used for thewater-containing content according to the present invention, there canbe exemplified silicone oil, glycerin fatty acid ester, liquid paraffin(white oil) or edible fat and oil. Particularly preferred examplesinclude glycerin fatty acid esters such as intermediate-chain fatty acidtriglyceride, glycerin trioleate and glycerin diacetomonooleate, as wellas liquid paraffin and edible fat and oil. They do not easilyvolatilize, have been approved as food additives and, besides, areodorless and do not damage flavor of the content, which are advantages.

For the oily contents, further, there can be used water or a highlyhydrophilic ionic liquid.

As the lubricating liquid that can be favorably used for the emulsiontype fluid substances, there can be exemplified silicone oil, glycerinfatty acid ester, liquid paraffin and edible fat and oil. Among them,the most desired is a lubricating liquid that emulsifies spending aperiod of time. Among the above-mentioned substances, the lubricatingliquid that exhibits such a property is the one having a relativelylarge molecular weight. This is because the lubricating liquid having asmall molecular weight also has small molecules that are subject to beentrapped by the emulsion type fluid substance (in short periods oftime). For instance, most desirably, the silicone oil and liquidparaffin should have relatively large molecular weights, the glycerinfatty acid ester should have a large fatty acid group (not less than 8carbon atoms in the fatty acid) and a large number of fatty acid groupsthat are substituted (e.g., diglyceride, triglyceride and, specifically,intermediate-chain fatty acid triglyceride, glycerin triol, etc.), andthe edible fat and oil should have a large fatty acid group (not lessthan 16 carbon atoms in the chief fatty acid).

It is desired that the above lubricating liquid is added in an amount ofnot less than 3% by weight and, specifically, not less than 4% by weightrelative to the resin composition in order to satisfy the covering ratioF lying in the above-mentioned range. This is because if the amountthereof is small, the covering ratio F decreases and it becomesdifficult to maintain good slipping property on the inner surface of thecontainer. If the lubricating liquid is added in unnecessarily largeamounts, on the other hand, the formability is impaired or the containerproperties are adversely affected. Usually, therefore, the amountthereof is not more than 20% by weight and, specifically, not more than10% by weight.

In order to attain a desired covering ratio or to form a desired liquidfilm, moreover, the lubricating liquid may, further, be applied onto theresin composition that has been blended with the lubricating liquid.Upon applying the lubricating liquid onto the resin composition that hasalready been blended with the lubricating liquid, it is allowed toprevent or suppress the lubricating liquid that is applied fromdiffusing onto the inner surface side of the container to therebymaintain stable properties.

-   3. Other Additives.

The above resin composition may be blended with various additives knownper se., such as antioxidant, ultraviolet ray absorber or fillerdepending on the use of the containers. If no transparency is required,the resin composition may be blended with a coloring agent such aspigment or dye and, further, with crystallizing additives (inorganicoxide such as titanium oxide, various waxes, etc.).

However, the amounts of the additives should be maintained small so thatthe amount of the lubricating liquid in the composition is maintained inthe above-mentioned range, that the formability of the forming-resin isnot impaired and that the slipping property is not impaired on the innersurface of the container.

<Layer Structure of the Container>

The container of the present invention may have either a single-layerstructure or a multi-layer structure so far as the inner surface of thecontainer (part of the surface that comes in contact with the fluidcontent) is formed of a resin composition that contains theabove-mentioned lubricating liquid. Basically, however, the inner layerof the container should have a multi-layer structure formed of theabove-mentioned resin composition. That is, in the case of thesingle-layer structure formed of the above resin composition, thelubricating liquid contained in the resin composition is consumed alsoon the outer surface of the container. To maintain a sufficient degreeof slipping property, therefore, the lubricating liquid becomesnecessary in amounts larger than the required amount not only impairingformability and container property but also arousing such problems asstickiness and the like.

The multi-layer structure is such that the innermost layer is formed ofthe above-mentioned resin composition and the outermost layer is formedon the outer side thereof. As required, an intermediate layer may beformed between the two layers. The multi-layer structure can be appliednot only to the directly blown bottles but also to the plasticcontainers (e.g., polyester containers) in the same manner. In thedirectly blown bottles, however, it is necessary that the wholethickness of the container wall has been so adjusted as to assuresqueezing property.

In the case of the bottles for containing, for example, shampoos andconditioners, there can be employed the two-layer structure comprisingthe innermost layer of the above-mentioned resin composition and a layeron the outer side thereof of a high-density polyethylene.

Usually, the intermediate layer in the multi-layer structure is agas-barrier layer formed, preferably, by using an ethylene/vinyl alcoholcopolymer (saponified product of ethylene/vinyl acetate copolymer) or anaromatic polyamide and, specifically, by using an ethylene/vinyl alcoholcopolymer. That is, by using a gas-barrier resin as the resin forforming the intermediate layer, it is allowed to impart oxygen-barrierproperty to the intermediate layer. Specifically, the ethylene/vinylalcohol copolymer exhibits particularly excellent oxygen-barrierproperty and makes it possible to effectively suppress the content frombeing deteriorated by oxidation due to the permeation of oxygen, tomaintain excellent slipping property and, at the same time, to maintainexcellent preservability of the content.

The preferred thickness of the gas-barrier intermediate layer is,usually, in a range of 1 to 50 μm and, specifically, 9 to 40 μm.

If the above gas-barrier resin is to be used as the intermediate layer,it is desire that the intermediate layer is provided via adhesive resinlayers in order to enhance adhesion to the inner and outer layers and toprevent delamination. Thus the intermediate layer can be firmly adheredto the inner and outer layers. Adhesive resins used for forming theadhesive resin layers have been known per se. For example, there is useda resin that contains, in the main chain or the side chain thereof, thecarbonyl groups (>C═O) in an amount of 1 to 100 meq/100 g of the resinand, specifically, in an amount of 10 to 100 meq/100 g of the resin.Concretely, as the adhesive resin, there is used an olefin resingraft-modified with a carboxylic acid such as maleic acid, itaconic acidor fumaric acid or an anhydride thereof, or with an amide or an ester;an ethylene-acrylic acid copolymer; an ionically crosslinked olefincopolymer; or an ethylene-vinyl acetate copolymer. The adhesive resinlayers may have a thickness that produces a suitable degree of adheringforce and, usually, a thickness of about 0.5 to about 20 μm and,preferably, about 1 to about 8 μm.

In the container having the above multi-layer structure, a regrind layermay be formed neighboring the outermost layer or the innermost layer bymixing the scrap resin that generates at the time of forming thecontainers and the virgin resin for forming the outermost layer. In thiscase, it is desired that the amount of the scrap resin is about 10 toabout 60 parts by weight per 100 parts by weight of the outermost virginlayer from the standpoint of reusing resources yet maintainingformability. The thickness of the layer neighboring the outermost layermay vary depending on the size of the packing container or the kind ofthe content, but should be such that the thickness of the container wallas a whole does not become unnecessarily large and that the scrap resincan be effectively utilized, and is, usually, set to be about 20 toabout 200 μm.

<Forming the Containers and Filling the Content>

A container and, specifically, a packing container for preserving thecontent for long periods of time, is formed by using the above-mentionedresin composition and a resin or a resin composition for forming layersother than the inner surface, by forming a preform such as pipe, testtube, sheet or film by the extrusion molding or the injection moldingthat has been known per se. depending on the shape of the container, andby forming the preform into the container in the form of a bottle, cupor bag by the blow forming, the vacuum forming such as plug-assistforming or by the secondary forming or the secondary working such assticking in the form of a bag. With the direct-blow forming, inparticular, a preform in the shape of a pipe having a predeterminedlayer structure is blow-formed with its one end closed to obtain acontainer.

In the case of the containers such as cups and trays for temporarilycontaining the contents, the containers are directly formed by theextrusion molding or the injection molding.

The containers of the present invention formed as described above arecapable of directly containing the contents therein without conductingthe after-treatment, specifically, with the lubricating liquid.Therefore, the containers can be produced in high yields. Further, sincethe innermost layer holding the lubricating liquid is firmly adhered tothe neighboring base material, there is no such probability that theinnermost layer may peel off providing a very high degree of safety.

In the case of the packing containers for preserving the contents forlong periods of time, further, a hot-filling method is employeddepending on the kinds of the fluid contents (e.g., sauce and ketchup)to fill the containers with the content while heating it at a hightemperature (70° C. or higher) to, at the same time, sterilize thecontent. When the hot-filling method is employed, too, the container ofthe present invention maintains excellent slipping property for extendedperiods of time, which is a great advantage of the present invention.

EXAMPLES

The invention will now be described by way of Examples.

Described below are a variety of properties, methods of measuringproperties and resins used for forming the containers (bottles) inExamples described below.

In the following measurement, the solid-liquid interface analyzer thatwas used was a solid-liquid interface analysis system, DropMaster 700,(manufactured by Kyowa Kaimen Kagaku Co.).

-   1. Measuring the Covering Ratio with Immiscible Liquid.

A test piece measuring 10 mm×60 mm was cut out from the body portion ofa bottle of a volume of 500 g prepared by a method described later.Under a condition of 23° C. 50% RH and by using the solid-liquidinterface analyzer, the test piece was fixed thereto in a manner thatthe inner layer of the test piece was facing upward. Three microlitersof pure water was placed on the test piece to measure the water contactangle θ. By using the obtained water contact angle, a covering ratio Fwith the lubricating liquid on the inner surface of the bottle was foundaccording to the following formula (1),

F=(cos θ−cos θ_(B))/(cos θ_(A)−cos θ_(B))  (1)

-   -   wherein θ is a water contact angle on the container surface        (inner surface) formed of the resin composition that forms the        container inner surface,    -   θ_(A) is a water contact angle on the immiscible liquid        (lubricating liquid), and    -   θ_(B) is a water contact angle on the forming-resin.

In finding the covering ratio F with the lubricating liquid, thefollowing water contact angles were used as the values θ_(A) and θ_(B).

θ_(B): 100.1° (value of a high-pressure low-density polyethylene(MFR=0.3) alone)

-   -   θ_(A): 80.3° (value of an intermediate-chain fatty acid        triglyceride on a liquid film)    -   θ_(A): 59.6° (value of a glycerin diacetomonooleate on a liquid        film)    -   θ_(A): 77.7° (value of a glycerin trioleate on a liquid film)

-   2. Measuring the Slip-Down Speed of the Content.

A Kewpie-Half (Japanese Agricultural Standards: Creamy Dressing forSalads, manufactured by Kewpie Co.) was used as the sample content inthe container.

A test piece measuring 20 mm×70 mm was cut out from the body portion abottle of a volume of 500 g formed by the method described later. Underthe condition of 23° C. 50% RH and by using the solid-liquid interfaceanalyzer, the test piece was fixed thereto in a manner that the innerlayer of the test piece was facing upward. 70 Milligrams of theKewpie-Half was placed on the test piece, the falling behavior on aninclination of 45° was photographed by using a camera, the fallingbehavior was analyzed, and the falling speed was calculated from theplots of moving distance vs. time. The falling speed was used as anindex of falling property. The larger the value of the falling speed,the more excellently the content falls down.

-   3. Testing the Amount Remaining in the Bottle.

As sample contents in the container, there were used (A) Okonomi Sauce(manufactured by Otafuku Sauce Co.) and (B) Kewpie-Half (manufactured byKewpie Co.).

The bottle of a volume of 500 g formed by the method described later wasfully filled with (A) the Okonomi Sauce or (B) the Kewpie-Half as thecontent, and was hermetically sealed with a sealing foil. Thetemperature of the content at the time of filling was 70° C. when (A)the Okonomi Sauce was filled and 23° C. when (B) the Kewpie-Half wasfilled.

After the bottle has been filled with the content, the sealing foil wasremoved from the bottle, a cap was fitted thereto, and 400 g of thecontent was squeezed out at room temperature. Thereafter, the bottle wasinverted and was left to stand at room temperature for 2 hours.

After left to stand, the squeezing operation was repeated for every 2minutes with the bottle being inverted and, after 20 minutes havepassed, the weight (weight of the content remaining+weight of thebottle) was measured. After the measurement, the content remaining inthe bottle was washed away with water, the bottle after washed wasmeasured for its weight, and a difference in the weight was found andwas regarded to be the remaining amount. The smaller the remainingamount, the more excellent the slipping property on the inner surface ofthe bottle.

-   4. Measuring the Ratio of Inner Layers of the Bottle.

By using a polarization microscope, the layer constitution was observedon the horizontal cross section of the body portion at a position 50 mmabove the bottom of the multilayer bottle formed by the method describedlater to thereby find the layer constitution in the body portion of thebottle. The layer constitution was observed at positions of 0°, 90°,180° and 270° relative to the cross section, and an average value in thefour directions was regarded to be the layer constitution of the bottle.

-   5. Measuring the Shapes of the Inner Surfaces of the Bottles.

The inner surface of the body portion of the multilayer bottle formed bythe method described later was measured for its surface shape by usingan atomic force microscope (NanoScope III, manufactured by DigitalInstruments Co.). The measuring conditions were as described below.

Cantilever: resonance frequency f₀=363 to 392 kHz, spring constant k=20to 80 N/m

Measuring mode: tapping mode

Scanning rate: 0.6671 Hz

Scanning range: 100 μm×100 μm

Number of scanning lines: 256

A mean square surface roughness RMS was found from the obtained data ofthe three-dimensional shape. By using a software (Nanoscope: Version5.30r2) attached to the atomic force microscope, the data of thethree-dimensional shape were converted into binary data of the portions(dents) lower than the center surface and of the portions(protuberances) higher than the center surface to obtain thetwo-dimensional data to thereby calculate the distribution of higherportions (protuberances) (i.e., to calculate the number of protuberancesand average area thereof). Here, the portions (dents) lower than thecenter surface are shown in black and the portions (protuberances)higher than the center surface are shown in white.

<Properties of the Fluid Contents>

Kewpie-Half (produced by Kewpie Co., viscosity=1260 mPa·s)

Okonomi Sauce (produced by Otafuku Co., Viscosity=560 mPa·s)

Here, the contents were measured for their viscosities at 25° C. byusing a tuning fork oscillator type viscometer SV-10 (manufactured by A& D Co.).

Example 1

The following resins were provided for forming the layers.

Resin for forming the innermost layer:

A resin composition comprising a high-pressure low-density

polyethylene (LDPE, MFR=0.3) and an intermediate-chain fatty acidtriglyceride at a ratio of 97/3 (wt %).

Resin for forming the outermost layer:

Low-density polyethylene (LDPE)

MFR: 0.3 g/10 min.

Density: 0.92 g/cm³

Resin for forming the second inner layer:

Low-density polyethylene (LDPE)

MFR: 0.3 g/10 min.

Density: 0.92 g/cm³

Resin for forming the adhesive layers:

Maleic anhydride-modified polyethylene

Resin for forming the gas-barrier layer:

Ethylene-vinyl alcohol copolymer (density, 1.19 g/cm³; Tg, 69° C.)

A five-kind-six-layer multilayer bottle having a volume of 500 g andweighing 20 g was prepared by a known direct-blow-molding method at ametal mold temperature of 20° C. by feeding the innermost layer-formingresin pellets to a 30-mm extruder, feeding the outermost layer-formingresin pellets to a 40-mm extruder, feeding the second innerlayer-forming resin pellets to a 50-mm extruder, feeding the adhesivelayer-forming resin pellets to a 30-mm extruder A, feeding thegas-barrier layer-forming resin pellets to a 30-mm extruder B, and byextruding a molten parison through a multilayer die head heated at 210°C.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

The layer constitution in the body portion of the bottle was as follows:

Outermost layer: 60 μm

Adhesive layer: 10 μm

Gas-barrier layer: 20 μm

Adhesive layer: 10 μm

Second inner layer: 250 μm

Innermost layer: 110 μm (innermost layer ratio, 24%)

Example 2

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the intermediate-chain fatty acid triglyceride at a ratioof 95/5 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 24%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

FIGS. 1A and 1B show the measured results of the shape of the innersurface of the bottle. FIG. 1A shows an image of before being convertedinto binary data and FIG. 1B shows an image of after having beenconverted into binary data.

Example 3

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the glycerin trioleate at a ratio of 97/3 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 22%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid and content slip-down speed. The results were as shownin Table 1.

Example 4

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the glycerin trioleate at a ratio of 95/5 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 22%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed and amount of the contentremaining in the bottle. The results were as shown in Table 1.

Example 5

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the glycerin diacetomonooleate at a ratio of 97/3 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 22%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid and content slip-down speed. The results were as shownin Table 1.

Example 6

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the glycerin diacetomonooleate at a ratio of 95/5 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 22%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed and amount of the contentremaining in the bottle. The results were as shown in Table 1.

Example 7

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3), the linear low-density polyethylene (LLDPE, MFR=2.2, meltingpoint=60° C., lowly crystalline) and the intermediate-chain fatty acidtriglyceride at a ratio of 82/15/3 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 25%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Example 8

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3), the linear low-density polyethylene (LLDPE, MFR=2.2, meltingpoint=60° C., lowly crystalline) and the intermediate-chain fatty acidtriglyceride at a ratio of 80/15/5 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 25%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Example 9

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3), the linear low-density polyethylene (LLDPE, MFR=2.2, meltingpoint=60° C., lowly crystalline) and the intermediate-chain fatty acidtriglyceride at a ratio of 67/30/3 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 25%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Example 10

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3), the linear low-density polyethylene (LLDPE, MFR=2.2, meltingpoint=60° C., lowly crystalline) and the intermediate-chain fatty acidtriglyceride at a ratio of 65/30/5 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 25%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Comparative Example 1

A multilayer bottle was formed in the same manner as in Example 1 butusing the high-pressure low-density polyethylene (MFR=0.3) as the resinfor forming the innermost layer. The innermost layer ratio in the bodyportion of the bottle was 24%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

FIGS. 2A and 2B show the measured results of the shape of the innersurface of the bottle. FIG. 2A shows an image of before being convertedinto binary data and FIG. 2B shows an image of after having beenconverted into binary data.

Comparative Example 2

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the intermediate-chain fatty acid triglyceride at a ratioof 99.9/0.1 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 24%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Comparative Example 3

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the intermediate-chain fatty acid triglyceride at a ratioof 99.5/0.5 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 24%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Comparative Example 4

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the intermediate-chain fatty acid triglyceride at a ratioof 99/1 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 23%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

Comparative Example 5

As the resin for forming the innermost layer, there was provided a resincomposition comprising the high-pressure low-density polyethylene(MFR=0.3) and the intermediate-chain fatty acid triglyceride at a ratioof 98/2 (wt %).

A multilayer bottle was formed in the same manner as in Example 1 butchanging the resin for forming the innermost layer into the abovecomposition. The innermost layer ratio in the body portion of the bottlewas 23%.

The thus prepared bottle was measured for its covering ratio with theimmiscible liquid, content slip-down speed, amount of the contentremaining in the bottle and shape of the inner surface of the bottle.The results were as shown in Table 1.

FIGS. 3A and 3B show the measured results of the shape of the innersurface of the bottle. FIG. 3A shows an image of before being convertedinto binary data and FIG. 3B shows an image of after having beenconverted into binary data.

TABLE 1 Constitution of resin composition of the surface to where thecontent comes in contact (wt %) Liquid Content Intermediate- coveringslip-down chain fatty acid Glycerin Diaceto- ratio speed LDPE LLDPEtriglyceride trioleate monooleate F mm · min⁻¹ Example 1 97 3 0.36 1.88Example 2 95 5 0.46 3.26 Example 3 97 3 0.37 1.81 Example 4 95 5 0.803.06 Example 5 97 3 0.74 1.55 Example 6 95 5 1 6.62 Example 7 82 15 30.26 1.27 Example 8 80 15 5 0.91 6.79 Example 9 67 30 3 0.29 1.02Example 10 65 30 5 0.91 6.80 Comp. Ex. 1 100 0 0.34 Comp. Ex. 2 99.9 0.10.03 0.16 Comp. Ex. 3 99.5 0.5 0.05 0.21 Comp. Ex. 4 99 1 0.09 0.22Comp. Ex. 5 98 2 0.25 0.25 Remaining amount Measurement of surface shapein the bottle (g) (100 μm × 100 μm) (A) (B) Ave. area of Okonomi Kewpie-Number of protuberances RMS sauce Half protuberances μm² nm Example 1 —4.9 97 54.18 87.9 Example 2 4.9 6.2 83 63.12 88.8 Example 3 — — — — —Example 4 6.3 — — — — Example 5 — — — — — Example 6 3.0 — — — — Example7 — 4.7 81 62.55 84.8 Example 8 — 3.3 32 161.71 164.8 Example 9 — 5.5 6775.92 134.2 Example 10 — 5.1 32 159.45 138.7 Comp. Ex. 1 11.4 9.5 16133.46 52.0 Comp. Ex. 2 10.9 10.1 152 35.76 48.4 Comp. Ex. 3 10.8 9.3 13938.15 72.3 Comp. Ex. 4 11.0 8.0 101 49.50 94.7 Comp. Ex. 5 12.3 7.9 11846.01 77.3

(Consideration)

It is learned from Table 1 above if the liquid covering ratio is notmore than 0.25 on the surface that comes in contact with the content,the content slip-down speed is small and the slipping property is poor.If the liquid covering ratio is not less than 0.26, on the other hand,the content slip-down speed increases and the slipping property becomesvery favorable. From the results of testing the amounts remaining in thebottles, further, if the container has the liquid covering ratio of notless than 0.26 on the surface that comes in contact with the content,the amount of the content that remains becomes smaller than the amountthat remains in the container having the liquid covering ratio of notmore than 0.25. In this case, therefore, the slipping property workseffectively to efficiently decrease the remaining amount of the content.

FIGS. 2A and 2B show the shape of the inner surface of the bottle ofwhen the composition contains no liquid in the surface that comes incontact with the content. In this case, fine ruggedness is confirmed,but small dents are distributed or are present in very large amounts.

FIGS. 3A and 3B show the shape of the inner surface of the bottle ofwhen the liquid covering ratio is 0.25 on the surface that comes incontact with the content. In this case, it is confirmed that the dentsare having sizes larger than those of FIGS. 2A and 2B. However, it isalso confirmed that the dents are much isolated and are littlecontinuous. Namely, it is considered that the liquid has not been heldin amounts sufficient for covering the surface of the inner layer of thecontainer.

FIGS. 1A and 1B show the shape of the inner surface of the bottle ofwhen the liquid covering ratio is 0.46 on the surface that comes incontact with the content. In this case, it is confirmed that theisolated dents are decreased as compared to those of FIGS. 3A and 3B,and the dents are very much continuing.

From these Figures, it is learned that if the liquid covering ratio islarge, the dents become highly continuous. The resin composition forforming the innermost layer of the container comprises only theforming-resin and the liquid. It is, therefore, considered that at thetime of forming the container, the dents are formed in the surface asthe forming-resin and the liquid undergo the phase separation.

DESCRIPTION OF REFERENCE NUMERALS

10: multilayer plastic container (bottle)11: neck portion13: shoulder portion15: body wall17: bottom wall19: metal foil20: cap

1. A container for containing fluid substance as a content, wherein:said container has a multilayered structure that includes, as anintermediate layer, a gas-barrier layer formed of an ethylene/vinylalcohol copolymer; an inner surface of said container that comes incontact with said fluid substance is formed of a resin composition thatcontains a resin for forming and a lubricating liquid that is immisciblewith said fluid substance and works to improve the slipping property tosaid fluid substance; said resin composition contains said lubricatingliquid in an amount of not less than 5% by mass; and the inner surfaceof said container is covered with, the lubricating liquid at a ratio Frepresented by the following formula (1),F=(cos θ−cos θ_(B))/(cos θ_(A)−cos θ_(B))  (1) wherein θ is a watercontact angle on the inner surface of the container formed by said resincomposition, θ_(A) is a water contact angle on said lubricating liquid,and θ_(B) is a water contact angle on said resin for forming, of notless than 0.46.